I was thinking you may have been using Linux and a samba/cifs share in which case a locking problem was the likely issue. This is apparently not the case. What I would suggest is a couple of tests. First, create a new library on your local machine and add a book. If this works okay create a new library on your NAS and add a book. If this works then the problem is likely a corrupted database. You should be able to fix this by using the restore database function from the library maintenance menu.
Let us know how you go.
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